CN1285651C - Macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin and its preparing process - Google Patents
Macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin and its preparing process Download PDFInfo
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- CN1285651C CN1285651C CN 200510024419 CN200510024419A CN1285651C CN 1285651 C CN1285651 C CN 1285651C CN 200510024419 CN200510024419 CN 200510024419 CN 200510024419 A CN200510024419 A CN 200510024419A CN 1285651 C CN1285651 C CN 1285651C
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Abstract
The present invention relates to macroporous crosslinking sulfonic acid perfluoroalkyl polystyrene ion exchange resin and a preparation process thereof. The structural formula of the ion exchange resin is disclosed in the specification, wherein p equals 0, 1, 2, 3 or 4, the ration of x to y is 98 to 20:2 to 80, and the ration of (x-z) to z is 0 to 80:100 to 20. The structural formula is prepared by reacting omega-halosulfonyl perfluoroacyl peroxide with macroporous crosslinking polystyrene resin by hydrolysis and acidification. The ion exchange resin has the advantages of high acidity, large specific surface area, accessibility to the active center, high thermal stability, easy synthesis, etc.; the ion exchange equivalent of the ion exchange resin is from 0.7 to 2.2 mmol/g; the ion exchange resin can be used for the fields of organic catalysis, environmental protection, etc.
Description
Technical field
The present invention relates to a kind of functional high molecule material and preparation method thereof, particularly macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin and preparation method thereof.
Background technology
Large hole cation exchanger resin has the history of four more than ten years, is widely used in gas phase or liquid phase adsorption catalysis, ion-exchange, fields such as sewage disposal.Zeo-karb mainly contains superpower acid type, strong acid type, several big classes of weak-type.Superpower acid type Zeo-karb mainly is a perfluorinated sulfonic acid ion exchange resin, as the Nafion series plastics of Dupont company production; Strongly acidic cation-exchange is mainly the polystyrene type sulfonate resin, as Rom ﹠amp; The Amberlyst series plastics that Hass company produces; The weak-type Zeo-karb is mainly polystyrene carboxylic acid, series plastics such as phosphoric acid.
Large hole cation exchanger resin is made up of many agglomerating microballoons and the macropore that is scattered here and there on every side thereof; It is big to have specific surface, and the active centre is easy to approaching, and exchanging equivalent is big, is easy to produce advantages such as low price; Its shortcoming be acidity a little less than, thermostability is relatively poor.The relatively poor root of these resin thermostabilitys is to take off sulfonic acid more than 120 ℃ easily.The thermostability and the research report of strength of acid that are intended to improve them are a lot.One of them method is exactly the binding ability that increases sulfonic group or contain sulfonic acid group substituting group and phenyl ring, such as introduce drawing electron groups such as halogen, nitro, ethanoyl on phenyl ring, takes off the purpose that the sulfonic acid temperature reaches raising resin thermostability thereby improve; And for example sulfonic acid group is connected on the phenyl ring by fatty carbon chain, also can improve the thermostability of resin, but the strength of acid of resin dies down obviously thereupon; Again with its sulfonation, so also can improve the thermostability of resin behind the spherome surface of polyethylene being received polystyrene or polyvinyl chloride that also has; The somebody directly with fluorine gas with macroporous polystyrene sulfonate resin perfluorination, the perfluor super acid resin of generation has both excellent thermostability and naturally near the superpower acidity of Nafion.But it is inflammable fluoridizing with element fluorine, explosive, and the operation of severe toxicity, the degraded of main chain are also unavoidable.
Nafion perfluorinated sulfonic acid series plastics thermostability is better than the macroporous cross-linked polystyrene sulfonate resin, has been widely used in fuel cell membranes, organic catalysis etc.Perfluorinated sulfonic acid ion exchange resin swelling in polar solvent is difficult to swelling in non-polar solvent.When as solid acid catalyst, because specific surface area is little, the active centre is not accessible, thereby catalytic activity is lower, has limited the scope of catalytic applications.Add that synthesis technique is loaded down with trivial details, blowdown is more, reason such as cost an arm and a leg, and it is restricted greatly that it is applied.In recent years, in order to overcome the above-mentioned shortcoming of Nafion, Dupont company successfully develops the Nafion resin attached to SiO
2The matrix material of nano grain surface, its specific surface area are thousands of times of Nafion, have improved catalytic activity greatly, but exchanging equivalent is reduced to about 10% of Nafion greatly.
As mentioned above, but the degree of closeness of strength of acid, thermostability, active center, production difficulty or ease are four big important indicators of comprehensive evaluation ion exchange resin.Macroporous cross-linked polystyrene sulfonate resin and perfluorinated sulfonic acid ion exchange resin respectively have superiority, but none satisfies whole four indices.In decades, Zeo-karb qualitative leap almost do not occur with regard to its structure type.Above-mentioned two resinoids are independent development separately, only improves the shortcoming of self in the finite space, does not but have the breakthrough of essence on method and product, and this is the bottleneck place of current Zeo-karb development.
Summary of the invention
The present invention provides a kind of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin and preparation method thereof.Its objective is perfluor and two not fluorine-containing resinoid constitutional featuress are combined together, produce the fluorine-containing sulfonic acid ion exchange resin of a kind of part, make it have the advantage of macroporous polystyrene type sulfonate resin and perfluorinated sulfonic resin concurrently and overcome both shortcoming.A promptly synthetic class has superpower acidity concurrently, high thermal stability, and bigger serface, the active centre is accessible, is easy to the Zeo-karb of advantages such as synthetic and low price.
Its structural unit of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin of the present invention is shown below:
P=0,1,2,3 or 4; X: y=98~20: 2~80; (x-z): z=0~80: 100~20.
Macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin of the present invention is to adopt macroporous cross-linked polystyrene resin and omega peroxide of perfluorin-acyl sulfonyl halide reaction to make macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin earlier, makes through hydrolysis and acidifying then.
The preparation method of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin of the present invention is as follows:
1) preparation of the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide:
(1) with the preparation method of sodium peroxide or barium peroxide: in churned mechanically glass reaction bottle is housed, add 20~80 milliliters of organic solvents, and reaction flask placed ice bath between-20~0 ℃, the sodium peroxide or barium peroxide and the ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides liquid that under agitation add finely powdered successively, mol ratio=2: 0.5~2 of ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides and sodium peroxide or barium peroxide wherein, continuation stirring reaction stopped reaction after 4 hours, filter rapidly, use 5wt%NaHCO successively
3The aqueous solution and distilled water wash filtrate, and add anhydrous sodium sulphate and fully shake up, in cryostat, leave standstill 30 minutes after, obtain the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide;
Or (2) are with caustic alkali and production of hydrogen peroxide method: the 10wt%~aqueous solution of 20wt% caustic alkali and the aqueous hydrogen peroxide solution of 30wt% are added with 2: 1~2 mol ratio be equipped with in the churned mechanically two neck glass reaction bottles, slowly open stirring after adding 20~80 milliliters of organic solvents, and reaction flask immersed in the ice bath, temperature remains between-20~0 ℃, under stirring fast, add the ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides liquid of metering, wherein ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides, NaOH and H in advance
2O
2Mol ratio=after 2: 2: 1~2,2 minutes, stop to stir, make the reaction mixture layering complete, oil reservoir is used 5wt%NaHCO successively
3The aqueous solution and distilled water wash add anhydrous sodium sulphate and fully shake up, in ice bath, leave standstill 30 minutes after, obtain the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide, wherein organic solvent is CClF
2CCl
2F, CH
2Cl
2Or CHCl
3, caustic alkali is lithium hydroxide, sodium hydroxide or potassium hydroxide;
2) preparation of macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin:
The polystyrene resin of macro porous crosslinking is immersed CH
2Cl
2Or CH
2ClCH
2Swelling among the Cl; be made into 5wt~20wt% concentration; under stirring and nitrogen protection; drip the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide; the mol ratio of the polystyrene resin reaction of this omega peroxide of perfluorin-acyl sulfonyl halide and macro porous crosslinking is 1: 50~0.2; the dropping time is 1~10 hour; temperature of reaction is-10~30 ℃, drip the back and continue reaction 3~48 hours, after reaction finishes after filtration; washing; be dried to constant weight, promptly get macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin, wherein the macroporous cross-linked polystyrene cross-linkage of resin is 2%~80%; the aperture is at 2~100nm, and surface-area is at 10~1000m
2/ g, pore volume is at 0.1~3cm
3/ g;
3) hydrolysis of macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin:
With the hydrolysis in the caustic solution of 10~30%wt of macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin, hydrolysis temperature is 60~90 ℃, hydrolysis time is 4~10 hours, obtain an alkali metal salt of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin, wherein caustic alkali is LiOH, NaOH or KOH;
4) acidifying of an alkali metal salt of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin:
Place the inorganic aqueous acid of 1~6mol/L to carry out proton exchange an alkali metal salt of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin, exchange after 15~48 hours after filtration, washing, vacuum-drying is to constant weight, promptly obtain macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin, wherein mineral acid is HCl, H
2SO
4Or HNO
3
Macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin of the present invention has perfluorinated sulfonic acid functionalization side chain similar with Nafion and suitable thermostability, be typical polymer super acids, and have specific surface area suitable and accessible active centre with the macroporous cross-linked polystyrene sulfonate resin.Macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin of the present invention can be used for organic catalysis, fields such as environment protection.
Description of drawings
The infrared spectrogram of Fig. 1 macroporous cross-linked polystyrene resin (a) and macro porous crosslinking p-perfluor-[1-(2-sulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin (b);
The thermogravimetric analysis of Fig. 2 macroporous cross-linked polystyrene resin (a) and macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene ion exchange resin (b).
Embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
1) CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2The preparation of F solution: in the cryosel bath with-15 ℃ of 100ml reaction flask immersions.Under slowly stirring, add the 10wt% aqueous sodium hydroxide solution of 8.0ml, the 30wt% hydrogen peroxide of 1.15ml and 50ml CCl
2FCClF
2, stir after 5 minutes, add perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl fluoride FO of 6.92g rapidly
2SCF
2CF
2OCF (CF
3) COF, reaction was carried out 2 minutes, stopped then stirring, and made the reaction mixture layering complete, and oil reservoir is successively used 5wt%NaHCO
3Behind the aqueous solution and the distilled water wash, add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 23%, and the aperture is 18.7nm, and surface-area is 128m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.64cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CClF 100mmol perfluor-2-(2-fluorine nyl ethoxy) propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continues to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight, promptly gets macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin after reaction finished;
3) hydrolysis of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.71mmol/g.
Fig. 1 is the infrared spectrogram of macroporous cross-linked polystyrene resin (a) and macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin (b), compares with a, and b is at 1212cm
-1And 1243cm
-1CF appears in the place
2Absorption peak, at 1312cm
-1CF appears in the place
3Absorption peak; At 1038cm
-1The charateristic avsorption band of ehter bond appears in the place.Fig. 2 is the thermogravimetric analysis of macroporous cross-linked polystyrene resin (a) and macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin (b), compare with a, b a weightless peak occurs at 190 ℃, and this is that desulfonation group causes.
Embodiment 2:
1) CClF of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2The preparation of F solution: in the cryosel bath with-15 ℃ of 100ml reaction flask immersions.Under slowly stirring, add the 10wt% aqueous sodium hydroxide solution of 8.0ml, the 30wt% hydrogen peroxide of 1.15ml and 50ml CCl
2FCClF
2, stir after 5 minutes, add the perfluor of 10.24g-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl fluoride FO rapidly
2SCF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF, reaction was carried out 2 minutes, stopped then stirring, and made the reaction mixture layering complete, and oil reservoir is successively used 5wt%NaHCO
3Behind the aqueous solution and the distilled water wash, add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 23%, and the aperture is 18.7nm, and surface-area is 128m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.64cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CClF 100mmol perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continue to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight after reaction finished, and promptly gets macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
3) hydrolysis of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.36mmol/g.
Embodiment 3:
1) CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2The preparation of F solution: in the cryosel bath with-15 ℃ of 100ml reaction flask immersions.Under slowly stirring, add the 10wt% aqueous sodium hydroxide solution of 8.0ml, the 30wt% hydrogen peroxide of 1.15ml and 50ml CCl
2FCClF
2, stir after 5 minutes, add perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl fluoride FO of 6.92g rapidly
2SCF
2CF
2OCF (CF
3) COF, reaction was carried out 2 minutes, stopped then stirring, and made the reaction mixture layering complete, and oil reservoir is successively used 5wt%NaHCO
3Behind the aqueous solution and the distilled water wash, add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 35%, and the aperture is 21.8nm, and surface-area is 361m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.83cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CClF 25mmol perfluor-2-(2-fluorine nyl ethoxy) propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continues to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight, promptly gets macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin after reaction finished;
3) hydrolysis of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.57mmol/g.
Embodiment 4:
1) CClF of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2The preparation of F solution: in the cryosel bath with-15 ℃ of 100ml reaction flask immersions.Under slowly stirring, add the 10wt% aqueous sodium hydroxide solution of 8.0ml, the 30wt% hydrogen peroxide of 1.15ml and 50ml CCl
2FCClF
2, stir after 5 minutes, add the perfluor of 10.24g-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl fluoride FO rapidly
2SCF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF, reaction was carried out 2 minutes, stopped then stirring, and made the reaction mixture layering complete, and oil reservoir is successively used 5wt%NaHCO
3Behind the aqueous solution and the distilled water wash, add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 35%, and the aperture is 21.8nm, and surface-area is 361m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.83cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CClF 100mmol perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continue to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight after reaction finished, and promptly gets macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
3) hydrolysis of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.16mmol/g.
Embodiment 5:
1) CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2The preparation of F solution: in the cryosel bath with-15 ℃ of 100ml reaction flask immersions.Under slowly stirring, add the 10wt% aqueous sodium hydroxide solution of 8.0ml, the 30wt% hydrogen peroxide of 1.15ml and 50ml CCl
2FCClF
2, stir after 5 minutes, add perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl fluoride FO of 6.92g rapidly
2SCF
2CF
2OCF (CF
3) COF, reaction was carried out 2 minutes, stopped then stirring, and made the reaction mixture layering complete, and oil reservoir is successively used 5wt%NaHCO
3Behind the aqueous solution and the distilled water wash, add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 23%, and the aperture is 18.7nm, and surface-area is 128m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.64cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CClF 150mmol perfluor-2-(2-fluorine nyl ethoxy) propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continues to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight, promptly gets macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin after reaction finished;
3) hydrolysis of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.91mmol/g.
Embodiment 6:
1) CClF of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2The preparation of F solution: in the cryosel bath with-15 ℃ of 100ml reaction flask immersions.Under slowly stirring, add the 10wt% aqueous sodium hydroxide solution of 8.0ml, the 30wt% hydrogen peroxide of 1.15ml and 50ml CCl
2FCClF
2, stir after 5 minutes, add the perfluor of 10.24g-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl fluoride FO rapidly
2SCF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF, reaction was carried out 2 minutes, stopped then stirring, and made the reaction mixture layering complete, and oil reservoir is successively used 5wt%NaHCO
3Behind the aqueous solution and the distilled water wash, add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 23%, and the aperture is 18.7nm, and surface-area is 128m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.64cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CClF 150mmol perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continue to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight after reaction finished, and promptly gets macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
3) hydrolysis of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.50mmol/g.
Embodiment 7:
1) CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2The preparation of F solution: 50ml CCl will be housed
2FCClF
2The 100ml reaction flask immerse during-15 ℃ cryosel bathes, under slowly stirring, add the sodium peroxide of 3.12g and perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl fluoride FO of 6.92g
2SCF
2CF
2OCF (CF
3) COF, continue to stir stopped reaction after four hours, filter rapidly, use 5wt%NaHCO successively
3The aqueous solution and distilled water wash filtrate add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CClF of perfluor-2-(2-fluorine sulphonyl-oxyethyl group) propionyl superoxide
2CCl
2F solution;
2) preparation of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 23%, and the aperture is 18.7nm, and surface-area is 128m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.64cm
3/ g), 80mlCH
2ClCH
2Cl fed nitrogen 30 minutes, stirred, at 0 ℃ of CClF with 100mmol perfluor-2-(2-fluorine nyl ethoxy) propionyl superoxide
2CCl
2The F drips of solution is added in the flask, adds in about 6 hours, continues to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight, promptly gets macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin after reaction finished;
3) hydrolysis of macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-[1-(2-fluorine sulphonyl) oxyethyl group] ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-[1-(2-fluosulfonic acid) oxyethyl group] ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.73mmol/g.
Embodiment 8:
1) CH of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2Cl
2The preparation of solution: 50ml CH will be housed
2Cl
2The 100ml reaction flask immerse during-15 ℃ cryosel bathes, under slowly stirring, add the sodium peroxide of 3.12g and the perfluor of 10.24g-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl fluoride FO
2SCF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COF, continue to stir stopped reaction after four hours, filter rapidly, use 5wt%NaHCO successively
3The aqueous solution and distilled water wash filtrate add no sodium sulfate, shake up several minutes after, in ice bath, left standstill 30 minutes, obtain the CH of perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2Cl
2Solution;
2) preparation of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: in the 250ml flask, (degree of crosslinking is 23%, and the aperture is 18.7nm, and surface-area is 128m to add 5g macroporous cross-linked polystyrene resin
2/ g, pore volume are 0.64cm
3/ g), 80ml CH
2Cl
2, fed nitrogen 30 minutes, stir, at 0 ℃ of CH 100mmol perfluor-{ 2-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } propionyl superoxide
2Cl
2Drips of solution is added in the flask, adds in about 6 hours, continue to stir 10 hours at 0 ℃, and after filtration, washing was dried to constant weight after reaction finished, and promptly gets macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
3) hydrolysis of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin: place the 30ml30wt%NaOH aqueous solution in 80 ℃ of heating hydrolysis 6 hours 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluorine sulphonyl-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin, washing filtering, 65 ℃ of following vacuum-dryings, obtain the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin;
4) acidifying of the sodium salt of macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin:: the sodium salt of 5g macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene resin is placed 30ml6mol/L HCl solution, room temperature acidifying 36 hours, washing filtering, to constant weight, promptly obtain macro porous crosslinking p-perfluor-{ 1-[2-(2-fluosulfonic acid-oxyethyl group) propoxy-] } ethyl substituted polystyrene ion exchange resin 65 ℃ of following vacuum-dryings.Its exchanging equivalent is about 1.39mmol/g.
Claims (2)
2. the preparation method of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin according to claim 1 is characterized in that the preparation method is as follows:
1) preparation of the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide:
(1) with the preparation method of sodium peroxide or barium peroxide: in churned mechanically glass reaction bottle is housed, add 20~80 milliliters of organic solvents, and reaction flask placed ice bath between-20~0 ℃, the sodium peroxide or barium peroxide and the ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides liquid that under agitation add finely powdered successively, mol ratio=2: 0.5~2 of ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides and sodium peroxide or barium peroxide wherein, continuation stirring reaction stopped reaction after 4 hours, filter rapidly, use 5wt%NaHCO successively
3The aqueous solution and distilled water wash filtrate, and add anhydrous sodium sulphate and fully shake up, in ice bath, leave standstill 30 minutes after, obtain the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide; Wherein organic solvent is CClF
2CCl
2F, CH
2Cl
2Or CHCl
3
Or (2) are with caustic alkali and production of hydrogen peroxide method: the 10wt%~aqueous solution of 20wt% caustic alkali and the aqueous hydrogen peroxide solution of 30wt% are added with 2: 1~2 mol ratio be equipped with in the churned mechanically two neck glass reaction bottles, slowly open stirring after adding 20~80 milliliters of organic solvents, and reaction flask immersed in the ice bath, temperature remains between-20~0 ℃, under stirring fast, add the ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides liquid of metering, wherein ω-halogen sulphonyl perfluorocarboxylic acid carboxylic acid halides, NaOH and H in advance
2O
2Mol ratio=after 2: 2: 1~2,2 minutes, stop to stir, make the reaction mixture layering complete, oil reservoir is used 5wt%NaHCO successively
3The aqueous solution and distilled water wash add anhydrous sodium sulphate and fully shake up, in ice bath, leave standstill 30 minutes after, obtain the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide; Wherein organic solvent is CClF
2CCl
2F, CH
2Cl
2Or CHCl
3, caustic alkali is lithium hydroxide, sodium hydroxide or potassium hydroxide;
2) preparation of macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin:
The polystyrene resin of macro porous crosslinking is immersed CH
2Cl
2Or CH
2ClCH
2Swelling among the Cl; be made into 5wt~20wt% concentration; under stirring and nitrogen protection; drip the organic solution of omega peroxide of perfluorin-acyl sulfonyl halide; the mol ratio of the polystyrene resin reaction of this omega peroxide of perfluorin-acyl sulfonyl halide and macro porous crosslinking is 1: 50~0.2; the dropping time is 1~10 hour; temperature of reaction is-10~30 ℃, drip the back and continue reaction 3~48 hours, after reaction finishes after filtration; washing; be dried to constant weight, promptly get macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin, wherein the macroporous cross-linked polystyrene cross-linkage of resin is 2%~80%; the aperture is at 2~100nm, and surface-area is at 10~1000m
2/ g, pore volume is at 0.1~3cm
3/ g;
3) hydrolysis of macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin:
With the hydrolysis in the caustic solution of 10~30%wt of macro porous crosslinking halogen sulphonyl per-fluoroalkyl polystyrene resin, hydrolysis temperature is 60~90 ℃, hydrolysis time is 4~10 hours, obtain an alkali metal salt of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin, wherein caustic alkali is LiOH, NaOH or KOH;
4) acidifying of an alkali metal salt of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin:
Place the inorganic aqueous acid of 1~6mol/L to carry out proton exchange an alkali metal salt of macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene resin, exchange after 15~48 hours after filtration, washing, vacuum-drying is to constant weight, promptly obtain macro porous crosslinking sulfonic acid per-fluoroalkyl polystyrene ion exchange resin, wherein mineral acid is HCl, H
2SO
4Or HNO
3
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